US 3275492 A
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United States Patent OPAL GLASS WITH A LOW COEFFICIENT 0F THERMAL EXPANSION Jean Leon Herbert, Saint Pierre-les-Nemours, Seine-et- Marne, France, assignor to Socit des Vel'reries Industrielles Runies du Loing, Paris, France No Drawing. Filed Jan. 29, 1962, Ser. No. 169,661 Claims priority, application France, Feb, 3, 1961, 851,644 6 Claims. (Cl. 1611) The present invention relates to opal glasses characterized by a low coefiicient of thermal expansion and a degree of opacity varying from a very light opalescense to a dense white opal. It is further concerned with an improved method of producing low expansion, heat resisting, opal glassware that does not require conventiona opacifying agents such as fluorides or phosphates.
An opal glass is an-otherwise normally transparent base glass containing an ingredient that dissolves during melting and precipitates in finely dispersed form during cooling or subsequent thermal treatment of the glass. Soda lime type base glass compositions are well adapted to production of opal glassware, but the resulting opal glasses and glass products are characterized by relatively high coefficients of thermal expansion on the order of 90 10-". Such glasses do not have suflicient resistance to thermal shock to permit their use in oven ware, and glass products having similar thermal requirements, except as the glassware is tempered subsequent to production. The expression coeflicient of expansion is used in its usual sense to mean the average linear expansion in cm./cm./ C. over a temperature range of 20 C. to 300 C. as measured in conventional manner.
It is well known that borosilicate type glasses are generally characterized by low coeificients of thermal expansion in the range of 25 to 50x1O- and consequent resistance to thermal shock. However, it has proven difficult to satisfactorily opacify such base glasses with conventional opacifying agents such as fluorides and phosphates. The high temperatures required to melt borosilicate glasses, as well as other characteristics of such glasses, create problems in production of a dense homogeneous opal glass. In particular, fluoride opacifying agents tend to volatilize during the glass melting process as Well as during subsequent forming of ware from the melt. As a result, there is an undue loss of opacifying agent, pollution of the surrounding atmosphere with obnoxious vapors, chemical attack on the refractory of the melting unit, and a generally transparent or pale opal product, especially adjacent the surface of the molded article. A variety of special opacifying agents for this type glass have been proposed, but have failed to adequately solve the problem of providing a homogeneous and otherwise satisfactory commercial opal glass product in a borosilicate base glass composition.
It is a primary purpose of the present invention to provide a means of overcoming these prior difliculties. A particular purpose is to provide opal glass compositions characterized by low coetficients of thermal expansion on the order of 25 to 50x10, and consequent thermal shock resistance. A further purpose is to provide a meth-. 0d of opacifying borosilicate base glasses and varying the degree of opacity from a light or pale opalescence to a dense white opal. Another purpose is to provide opacified borosilicate type glasses having modified viscosity characteristics and consequent improved working characteristics. A further purpose is to provide opal glass products having desirable thermal and mechanical shock characteristics as well as desirable acid resistance and electrical properties.
Opal glasses in accordance with the present invention are obtained by introducing into an alkali-borosilicate type glass, as hereafter described, an opacifying agent seleoted from the group consisting of the following metal oxides and mixtures thereof: ZnO, MgO, 0210, B210, NiO, CoO, MnO, CuO, such oxides being generically identified as R0 for convenience. The effective proportions of the various glass components, in mol percent as calculated from the glass batch, are within the following ranges:
the glass forming oxides B 0 and SiO;; are present in total amount of from 75 to 95%, the mol ratio of B 0 to SiO varying from 0.1 to 0.6,
the metal oxides identified above as opacifying agents (R0) are present in an amount totaling from 3 to 24%,
7 the monovalent modifying oxides, generically identified as R 0 and selected essentially from Li O, K 0, and Na O, are present in an amount totaling from 1 to 7%; the mol ratio between the content of these monovalent alkali ,metal oxides and the opacifying oxides, i.e. R O/RO, being from 0.1 to 1.0, except when Li O is selected as the modifying oxide in which case the ratio is from 0.07 to 1.5,
the content of alumina, A1 0 if that oxide is present, does not exceed 1%.
The glasses thus defined generally have coefiicients of thermal expansion within the range of 25 to 5O 10"' over the temperature range of 20 C. to 300 C.
The alkali metal oxide content in a particular glass will depend primarily on the degree of opacity desired and on the desired coeflicient of thermal expansion. The degree or density of opacity in a particular glass will generally decrease, assuming all other conditions equal, as the ratio between the alkali metal oxides and the opacifying oxides increases. Various physical properties of the present glasses, such as the coefiicient of thermal expansion, the temperature-viscosity relationship, the dielectric characteristics and the glass working range, may be varied by varying the alkali metal modifying and the opacifying oxides selected, the ratio between alkali metal oxides and opacifying oxides and the ratio between B O 'and SiO The degree or density of opacity in a glass will depend to some extent on the opacifying oxide selected. It will also depend on the ratio between the modifying alkali metal oxides and the opacifying oxides. In general, as this ratio increases the opal density decreases with the result that a paler opal is obtained.
In general, the opacifying agent will strike in, that is precipitate throughout the glass article, during production of the article by such methods as casting, blowing, molding and extruding. Where the opacifying agent strikes in slowly, or Where the glass article is quickly cooled before opacity develops, the glass will be thermally opacifiable, that is the opacifying agent will precipitate during a subsequent heat treatment of the article. The,
scoration on the glass surface simultaneously with such lermal opacification.
Prior commercial borosilicate glasses, which have a igh silica content and a coefficient of thermal expansion n the order of 30 10" between 20 and 300 'C., reuire extremely high Working temperatures.
lasses insofar as silica content and thermal coefficient of xpansion are concerned, but, in contrast, are adapted to eing worked, that is melted and formed intoglass ar- The relatively high tem- The presnt glasses are comparable to these prior commercial The present glasses require no special melting COlldi'. tions and may be melted in accordance with conventional borosilicate glass melting practice. Thus, theyymay be melted in a gas fired continuous glass melting unit at temiperatures of about 1450'to 1600 C., the particular melting conditions for any given glass being determined from its physicalproperties in the usual manner. ,7 Batch materials may also be of conventional nature as indicated in the subsequent specific examples.
The following exemplary compositions, shownboth in batch form and in oxide form as calculated both in percent by weight and mol percentfrom such batch composition,
will serve to further illustrate the .invention while notlimiting its scope. In particular, the examples illustrate the manner in'which opacity and :expansion maybe varied by selection of difierent constituent oxides and differing 1 proportions of such oxides.
Examples Batch Composition I II III Sand 100 100 100 33 7.7 .12. 7 11. 3 4. 6 1. 5 2. 1 Sodium Sulfate 6 V L 5 5- 6 Oxide Composition Weight M01 Weight Moi Weight M01 percent percent percent percent percent percent 63. 67. 2 64.4 68. 0 70. 7 74.0 29.0 26.4 29.7 27.0 13.2 11.8, 4.8 3.8 4.9 4.0 9.0 6.9 4. 5. 0 1. 9 1. 3 0. 6 0. 45 0. 9 0. 6 1.3 1.3 0.4 0.45 1.7 1.7. 0.39 0. 39 0. 16 r o/R0 0.68 0.21 0.33 i Exp. CoeL/CPXIO-L 38 i 32 The viscosity characteristicsv of the present glasses facilitaterefining of the glass during the melting operation.
They also enable to avoid the use of refining agents such as sodium sulfate which, at higher melting temperatures, would attack alumina containing refractory materials and thus lead to an undesirable increase in alumina content of the resulting glass. .While the conventional refining agent such as sulfates or halogen compounds may therefore be employed if desired, it has been found that the present.
glasses may normally be produced without addition of such fining agents.
A primary advantage of the present invention lies in the ability to produce a low expansion, opalborosilicate \glass without employing the conventional fluoride or phosphate opacifying agents. However, in certain cases it is advantageous to employ small amounts of known opacitying agents as a secondary or supplrnental agent in conjunction with the primary opacifying agent's described above. The amount of such secondary opacifying agent will be much smaller than that required where such agent is employed alone to produce opacity. Thus, the amounts of such secondary opacifying agents, if present, will normally not exceed about 4 mol percent F, 2 mol percent P 0 or 5 mol percent CeO these secondary agents being capable of use either individually or in combination.
The glasses of Examples I and II were melted at a temperature of 1580 C. A four mm. thick plate of glass I was a weak or pale opal; a similar plate of glass-H showed a much stronger degree of opacity; and glass 111 provided a still greater degree of opacity.
The following example illustrates; a glass that is transparent when handled under thesame conditions as pre-.
scribed for the glasses of the preceding examples. This becomes opacified by heat .treatment for, one hour, at 900 C.
; The following examples illustrate further compositions. 1n accordance with the invention, together with the expansion coeflicient and opal color of a glass produced from each composition.
Examples 1 Examples Batch Composition Oxides XV XVI XVII V lBis' IIBls M01 M01 M01 Percent Percent Percent 100 100 7. 74.1 75.6 80.3 4.25 1.39 13 .4 10.3 13.4 Sodium carbonate 3.45 1*.12 "7.7
10.0 Onde Composrtron Weight M01 Weight M01 1 2 Percent Pereen Percent Percent 0.6 1. 1.7 0.9 0.0 03.0 67.2 64.4 68.0 29.0 26.4 29.7 27.0 4.8 3.8 4.9 4.0 3.4 1.9 1.3 0.0 0.45 0.18 0.14 1.3 1.3 0.4 0.45 0.24 0.18 30 1 White 1 Dense. Opal light brown. Batch Composition Example III 1315 t Sand .Q. 100 Transparency of comparable glass 311216168 produced Bork, m 33 r Zinc oxide 12. mm the compositions of Examples XII to XV was meae calcium carbonate 11 .3 1red 1n terms of. lrght 'havmg a wave length of 530 m1- gog ssmm rgarboglate 1.1 :rons. The measurements were made on an apparatus I mm W e v fig gig i g zgi zgfig 3:3 giggg Oxide Composition M01 Percent M01 Percent 3% %8 Examples x11 x111 xrv 45 510 2-2 17- Eransparency '12-.-- 0.69 0.16 0.15
r Batch Composition Example IV Bis It W111 be. observed that the glass 'batches of the fore- 7 going examples may contain on the order of 5 to 6% of sand alkaline metal sulfates, and/or chlorides. However, the a g 7 glass obtained by melting any one of these batches will 40 5173 normally be found to contain less than 0.2% by weight swim carbon or Cl. In the event that it is desirable to avoid the O C h presence of sulfate or chloride ions entirely, glasses correnae omposlton tram Ma Percent spending to those shown in the examples may be melted 62 4 66 6 e from batches wherein other conventional raw materials 2 13 are employed in lieu of sulfates or chlorides, e.g. potas- -i f? V sium and sodium carbonates as given in following Ex- .10 1.7 amples I Bis to XV Bis.
Exam les Batch Compositions v Bls VI Bis VII Brs Oxide Composition. Weight M01 Weight Mol Weight M01 1 percent percent percent percent percent percent Examples Batch Compositions VIII Bis IX Bis X Bis XI Bis 18. 8 18. 8 003K, 1. 94 1. 94 1. 9.4 1. 94 COzNAL 2. 62 2. 62 2. 62 2. 62
Oxide Composition Weight Mol Weight M01 Weight M01 Weight M01 percent percent percent percent percent percent percent percent Examples Batch Compositions XII Bis XIII Bis XIV Bis XV Bis Sand 100 100 100 100 Boric oxide 22.9 19. 5 18.3 Boric acid 37. 2 Zine oxide 11. 4 11. 3 14. 1 Magnesium carbonate- 3. 28 5. 65 Calcium carbonate- 9. 90 Calcium nhnsnhate 4. 5 Potassium carbonate 3.97 1. 94 1. 94 Sodium carbonate 2. 4. 6. 4. 20
Oxide Composition Weight Mol Weight M01 Weight Mol Weight Mol percent percent percent percent percent percent In addition to the advantageous characteristics already described, glasses according to the invention also provide various other advantages. They are resistant to mechanical shock, probably due to homogeneity of the dispersed phase. They are also easy to effectively anneal, have good resistance to attack by water or acids, and possess desira ble dielectric properties, thus rendering them particularly useful in electronic applications.
When the opacification is developed within a glass article after its formation, it is possible to obtain a great precision of the degree of opacity 'by controlling the thermal treatment. It is thus possible to limit the dimensions of the diifusing particles in order to obtain for a given spectral light area, the desired diifuse reflection coefficient.
It is consequently possible to produce glass articles with the exactly convenient matching of the decoration and of the coloration and opacity of the support.
An example of a combined thermal treatment for opacification and enameling of a glass according to the invention, is given hereafter:
The glass has the following composition:
Weight Mol percent 99 oosim was BgO /SiO: =0.39.
RaO/RO =0.88. Exp. Coei. (10- =38.
A series of vessels is produced by pressing from the glass having the above composition. To these vessels different types of decoration are applied by decalcomania.
Thereafter the vessels are brought to a temperature from 750 to 780 C. for duration varying from one another between several minutes to one hour. The resulting articles present different opacities, increasing with the duration of the thermal treatment, and matching in the desired manner with the decoration chosen for each of them.
What is claimed is:
1. An opacifiable borosilicate glass composition having a coetficient of expansion on the order of 25 to 50 10" consisting essentially on a mol percent basis of:
(a) 10-27% (equivalent to about 12-30 weight per- Cent 0f B203 (b) 66-81% (equivalent to about 62-76 weight percent) of SiO (0) 324% of an opacifying agent (R0) selected from the group consisting of ZnO, MgO, CaO, BaO, NiO, MnO, C00, CuO and mixtures thereof,
(d) 17% alkali metal oxides (R 0) selected from the group consisting of Li O, K 0 and Na 0, and wherein there is an R O/R0 mol ratio of 0.1 to 1.0 when K 0 and Na O are present and a mol ratio of 0.07
to 1.5 when Li O is present.
Z. An opacifia ble glass composition as in claim 1 wherein there is contained A1 0 in an amount less than 1 mol percent.
3. An opacifiable glass composition as in claim 1 where- 1 the content of S plus Cl does not exceed about i 4. 'An opacifia'ble glass as in claim 1 containing further.
:condary opacifying agents selected from the group conto isting of up to 4% F, up to 2% P 0 and up ,to 5% 5. A method of producing an opal glass having a cofiicient of expansion on the order of to 10-' rhich comprises incorporating 3-24 mol percent of an equivalent to about 62-76 weight percent) of SiO;;, and 15 ,7% of an alkali metal oxide selected from the group.
consisting of Li O K- Q and Na Q and subjecting said glass to a heat treatmentto develop said opal glass.
References Cited by the Examiner UNITED STATES PATENTS 1,656,260 1/1928 Zeh 111-31 2,651,146 9/1953 'StOOkey 65-33 X, 2,920,971 1/1960 Stookey 6533 X 3,017,279 1/1962 Van Dolah 106-52 X I 3,057,691 10/1962 Veres 65-33 DONALL H. SYLVESTER, Primary Examiner.
G. MYERS, Assistant Examiner.
opal glass product made by the process of UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No,, 3,275,492 September 27, 1966 Jean Leon Herbert It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 4, line 48, after "This" insert glass column 8, line 27, for "Mol Percent", first occurrence, read Weight Percent columns 9 and 10, in the second table, under the heading "XIII Bis" and opposite "Magnesium carbonate", for "3.28" read 32,8 column 10, line 49, for "duration" read durations --c Signed and sealed this 22nd day of August 1967.
(SEAL) A est:
ERNEST W. SWIDER EDWARD J. BRENNER Anesting Officer Commissioner of Patents